Adducts of silicon hydride polysiloxanes and silanes having alkenyl radicals



United States Patent US. Cl. 260-465 12 Claims ABSTRACT OF THEDISCLOSURE A siloxane copolymer which is useful for rendering substrateswater repellent is disclosed. The siloxane copolymer has a formulawherein R and R are each alkyl or phenyl or their halogenatedderivatives; a is 0 to 2; b is 2 to 4; m is 2 to 99 mol percent of thesilicon atoms; n is 1 to 98 mol percent of the silicon atoms; 2 is 0 to97 mol percent of the silicon atoms; m-l-n-I-z is 6 to 200-0; x, y and dare each 0 to 2 and x-l-y is 0 to 2.

This is a division of application Ser. No. 402,941, filed Oct. 9, 1964.

This invention relates to siloxane copolymers which have silicon-bondedhydrogen atoms and silicon containing moieties bonded to the siliconatoms of the siloxane copolymer chain through alkylene radicals. Thesiliconcontaining moieties have triorganosilyl groups.

An object of the present invention is. to provide siloxane copolymersfrom silicon hydride siloxane polymers and alkenyl containing silanes.

Another object is to provide a siloxane copolymer which is curable witha catalyst.

Another object is to provide a siloxane copolymer which is a waterrepellent.

Other objects and advantages will become apparent from the followingdetailed description of the present invention and the appended claims.

This invention relates to a siloxane copolymer of the general formulawherein R is a monovalent radical selected from the group consisting ofalkyl radicals having from 1 to 12, inclusive, carbon atoms, halogenatedalkyl radicals having from 3 to 12 inclusive carbon atoms, phenylradicals and halogenated phenyl radicals, R is a monovalent radicalselected from the group consisting of alkyl radicals having from 1 to 6,inclusive, carbon atoms, halogenated alkyl radicals having from 3 to 6,inclusive, carbon atoms, phenyl radicals and halogenated phenylradicals, a has an average value of from O to 2 inclusive, b has a valuefrom 2 to 4 inclusive, m \has a value such that at least 2 mol percentof the silicon atoms have at least one radical and not more than 99 molpercent of the silicon atoms have at least one -(CH ,SiR,,'(OSiR');,radical, n has a value such that at least one mol percent of the siliconatoms have at least one hydrogen atom bonded to a silicon atom and notmore than 98 mol percent of the silicon atoms have at least one hydrogenatom bonded to a silicon atom, 2 has an average value of from O to amaximum value which is such that not more than 97 mol percent of thesilicon atoms have two R radicals per silicon atom, the sum of m+rt+z isfrom 6 to 2,000, x has an average value of from 0 to 2 inclusive, y hasan average value of from 0 to 2 inclusive, the sum of x+y is from 0 to2, inclusive, and d has a value of from 0 to 2, inclusive.

The siloxane copolymers of this invention can be either linearsiloxanes, cyclic siloxanes or mixtures of linear siloxanes and cyclicsiloxanes. The cyclic siloxanes can be composed of 2 to 99 mol percentof siloxane units of the unit formula R OS KCHZ)b lR' (OSlR 3)3-; 1 to98 mol percent of siloxane units of the unit formula and 0 to 97 molpercent of siloxane units of the unit formula R SiO. The mol percent isbased on the total mols of siloxane units present in the composition.One mole of a siloxane unit is equal to the formula weight of thesiloxane unit. Other units besides those discussed above can be presentin small amounts such siloxane units as 'a Hm w ah-slx The linearsilo-xanes are the preferred siloxanes of this invention. The siloxanesof this invention can also be a mixture of linear and cyclicpolysiloxanes. These mixtures can have an average formula wherein d willvary from 0 to 2. When d is 0, the polysiloxane copolymers areessentially cyclic polysiloxanes and when d is 2, the siloxanecopolymers are essentially linear polysiloxanes. When the value of d isbetween 0 and 2, the siloxane copolymers contain both linearpolysiloxanes and cyclic polysiloxanes in a ratio as indicated by d.Both the cyclic and linear siloxanes can be polymerized in a random orblock structure.

The siloxane copolymers of this invention must contain both In theseunits R is a monovalent radical such as alkyl radicals having from 1 to12 carbon atoms such as methyl, ethyl, propyl, 'pentyl, hexyl, octyl,dodecyl, cyclopentyl, cyclohexyl radicals, halogenated alkyl radicalshaving from 3 to 12 carbon atoms such as 3,3,3-trifiuoropropyl,bromohexyl, chlorocyclohexyl and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafiuorooctyl radicals, phenyl radicals and halogenated phenylradicals such as dichlorophenyl, fluorophenyl and bromophenyl radicals.In these units, R is a monovalent radical such as alkyl radicals havingfrom 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl,cyclopentyl and cyclohexyl, halogenated alkyl radicals having from 3 to6 carbon atoms such as 3,3,3-trifluoropropyl and bromocyclopentylradicals, phenyl radicals and halogenated phenyl radicals such aschlorophenyl, dibromophenyl and fluorophenyl radicals. The preferredradicals for R and R are methyl radicals.

In the R os iwHi)bSiR'.,(osiR' units, a is 0, l or 2, preferably a isor 1. The siloxane copolymer must have at least 1 triorganosilyl group.Thus, 11 cannot be more than 2. The alkylene radicals can be ethylene,propylene or butylene radicals. Thus b is 2, 3 or 4, preferably b is 2.

Examples of the above units are I I I 011205: OSiR units are OSlCHg,OSiCHgCH3, OSiC /CH2 CIIzCHz i i 03105115, OSiCHzCHzCFa, OSiCHgCEOSiCHKCIiDbCH;

III

and

OsiCHzCHzoc n In the R SiO units, the R is defined above. Examples of RSiO units are (CH SiO, (CH (CH CH )Si0,

4 (C H SiO, (C H (CH )SiO, (CF CH CH (CH )SiO, ti 11)( 3) s s) a z) (CHCH Si0 [CH (CH (CH )CiO and [CH (CH CiO.

The terminating siloxane units of the linear siloxanes have the unitformula R. I2)b s)a-A]x HySiOM In the terminating siloxane units the 2)b'a( 'a)a a and R are fully defined above. The terminating siloxane unitshave at least one R radical per unit and can have up to 3 R radicals perunit. The terminating siloxane unit can also have up to 2 hydrogen atomsbonded directly to the silicon atom. Thus, y can have a value from 0 to2. The terminating siloxane unit can also have up to two 2)b '4( '3)s aradicals. Thus, x can have a value from 0 to 2. The sum of x+y can varyfrom O to 2 depending upon the average number of hydrogen atoms and z)ba( 'a)a a radicals attached to the silicon atom of the terminatingsiloxane unit. Examples of terminating siloxane units are The siloxanecopolymers of this invention can be relatively low molecular weightpolymers consisting of at least 6 siloxane units or relatively highmolecular weight polymers consisting of up to 2,000 siloxane units. Thesiloxane copolymers with less than 6 siloxane units do not cure tousable products and those having more than 2,000 siloxane units are noteconomical to prepare. The most preferred siloxane copolymers containfrom 10 to 200 siloxane units. The siloxane copolymers can be prepared badding a silane of the formula CH =CH(CH SiR' (OSiR' where R and a aredefined above and 2 has a value of 0, 1 or 2, to a mixture of a platinumcatalyst and a silicon hydride polysiloxane of the unit formula 3-y IIIIII, y 0.5]d SIiO fiiO R D R z where R, y, z and d are defined above and1 has a value, such that at least 3 mol percent of the silicon atomshave at least one hydrogen atom bonded to a silicon atom.

The silanes operable in this procedure are well known in the art.Examples of these silanes are CHFCHSHO Si(CHa) 313, C H =OHSilOSi(CHa)s]z CH CuHs CH CHS'iOSKCEhh, CH2=CHCH2Si[OSi(CHa)]2 Si(CHa)3 H2cHscHzs iom (CH (C -H SiO, (CF CH CH (CH )SiO,

0141,0112) (CH )SiO and [CH (CH (CH )SiO.

The platinum catalyst can be in any form which is not basic in naturesuch as platinum on charcoal and platinum on alumina. Any platinumcatalyst which is basic will reduce the yield of product and willproduce polymers other than those described by this invention. A mixtureof platinum catalyst and silicon hydride polysiloxane is usuallypreheated to a temperature of 110 to 160 0., preferably 120 to 150 C.before the addition of the silane. These preheating temperatures are notcritical. The mixture need not be preheated before the addition of thesilane but because the reaction is usually exothermic and substantiallybegins at about 110 to 120 C., preheating is advantageous. When smallquantities of silane are used, preheating is usually not necessary butas larger quantities are used, preheating becomes very desirable. Thereaction is vigorous and the silanes being relatively low boiling cancause the system to build up pressure and/or cause flooding of thesystem. The silanes are thus usually added at a rate which is inverselyproportional to the quantity of silane to be added. The silane need notbe added to the polysiloxane. The polysiloxane can be added to thesilane. The mixture is usually agitated during the addition. After theaddition is completed, the mixture is raised to a temperature of 200 to220 C. to insure completion of the reaction and then cooled to roomtemperature or to some temperature less than 200 C. when the reaction isto be vacuum stripped.

The best results are obtained when the system is blanketed with an inertgas such as nitrogen. Some oxidation can occur at these reactiontemperatures although systems in which an inert gas is not used usuallyhave an insignificant amount of oxidation. The silane and siliconhydride polysiloxane do not require a solvent for carrying out thereaction but an organic solvent can be used. When the silicon hydridepolysiloxane is of a high molecular weight, a solvent solution of thesilicon hydride polysiloxane and/or silane is particularly advantageousas the viscosity of the system will be reduced and handling propertiesare improved. The organic solvent should permit the temperature ofreaction to be reached. The higher temperatures can be reached eitherwith higher boiling solvents or by using pressure. Examples of someoperable organic solvents are toluene, xylene, naphtha, organic esterssuch as butyl acetate, 2-ethylhexyl acetate, acetate of ethylene glycolmonomethylether, acetate of ethylene glycol monobutyl ether and organicketones such as methylethyl ketone and methylhexyl ketone.

After the reaction mixture has cooled to room temperature or to thestripping temperature, any remaining unreacted silanes and/or solventcan be removed by heat and vacuum. The catalyst can be removed by anysuitable means, such as filtering.

The siloxane copolymers of this invention have excellent shelfstabilities. These siloxanes have stable viscosities when stored with orwithout solvent over long periods of time. These siloxanes can also bemade into stable emulsions. The siloxane copolymers of this inventioncannot be stored with a curing catalyst, thus they form a two componentsystem for curing. The curing catalyst is added just before use. Thesiloxane copolymers of this invention can be used as water repellents.The siloxane copolymers are superior water repellents for fabrics andcan be applied to fabrics from an organic solvent solution, an aqueousemulsion and a consumer aerosol package. All of these applicationsprovide fabrics with good water repellency when cured with a catalyst ata temperature of from 30 C. to 260 C. The water repellency produced onthe fabric is durable and can withstand several washings. The waterrepellency of a fabric which has lost some of its effectiveness canreadily be renewed by any of the above treatments.

The siloxane copolymer used as a water repellent can be applied from asolvent solution using organic solvents such as toluene,perchloroethylene, hexane, acetone, isopropanol, ethanol and methanol.The fabric can be made water repellent by dipping in the solventsolution of the siloxane copolymer. The solvent solution of the siloxanecopolymer can be brushed on the fabric or applied in any otherconventional manner. The amount of pickup of siloxane copolymer ispreferably from 1 to 10 weight percent with from 1 to 3 weight percentbeing more commercially desirable.

The siloxane copolymer can also be applied to fabrics to provide waterrepellency from aqueous emulsions. The emulsions can be prepared in anyconventional manner using nonionic, anionic or cationic surfactants. Thenonionic surfactants are preferred. The most preferred surfactants arethe reaction product of ethylene oxide and acetylenic glycol known asSulfynol 465 made by Air Reduction Chemical Co. and trimethylnonylpolyethylene glycol other known as Tergitol TMN-6. The emulsion can beprepared to contain a wide concentration of siloxane copolymer. The mostpreferred concentration is from 5 to 40 Weight percent siloxanecopolymer. The emulsion can be applied to the fabric in any conventionalmanner. The fabric can be immersed in an emulsion, removed and dried.The water repellency is usually good when the amount of siloxanecopolymer pickup by the fabric is from 0.5 to 10 weight percent withfrom 0.5 to 3 weight percent being more commercially desirable.

The siloxane copolymer can be applied to fabrics to provide waterrepellency by spraying from aerosol packages. The siloxane copolymer canbe put into any conventional type of aerosol package. The siloxanecopolymer can be in any suitable organic solvent usually used withaerosol spray such as chlorothene, or perchloroethylene.

Conventional spray propellants such as dichlorodifluoromethane, Freon12, can be used. The amount of siloxane copolymer in the solventsolution is preferably from 1 to 20 weight percent. A spray of from 2 to60 seconds over an area of 0.2 to 0.6 square foot provides a fabric withgood water repellent properties. Usually only from 2 to 30 seconds issuflicient to provide maximum protection.

The siloxane copolymers are useful for making fabrics water repellentsuch as cotton, sateen, viscose, glass, nylon, Dacron, acetate, Arnel,cellulose triacetate, polyacrylonitrile (Orlon), synthetic polyesters ofterephthalic acid and ethylene glycol, copolymers of acrylonitrile andvinylidene chloride (Dynel), copolymers of vinyl chloride and vinylidenechloride, copolymers of vinyl acetate and vinyl chloride, Wool andlinen.

The siloxane copolymers are also useful as water repellents for paper,glass, leather, wood, masonry products and other substrates. Thesiloxane copolymers of this invention can also be used as lubricants andas hydrophobic fluids.

The most preferred siloxane copolymers of this invention are thosecontaining from 25 to 75 mol percent of siloxane units of the unitformula R osiiwHg)bsiR'.(0siR'3) and from 25 to 75 mol percent ofsiloxane units of the unit formula OSiR These siloxanes are particularlyuseful as water repellents for fabrics. The most preferred siloxanes arethose in which the sum of m+n+z is from 10 to 200.

The siloxane copolymers can be cured to durable films by catalystselected from the group consisting essentially of amines,aminoorganosilicon compounds, metal carboxylates, organic esters oftitanium and zirconium and alkyl tin carboxylates. The siloxanecopolymers are cured by heating at temperatures from 30 to 260 C.,preferably from 65 to 205 C. The amines which are operable are thosesuch as primary amines, secondary amines and tertiary amines. Theseorganic amines are well known to the art and can be obtainedcommercially. The aminoorganosilicon compounds can be silanes orsiloxanes such as (CH SlCH CH CH NH (CH3onswmomoHzNomomNm(C5H5)2Sl(CH2CHCH2NHz)3 a siloxane polymers having units as LaOSiCHzCHCH NHOHzOH NHr CHzHu SiO (CH CHZC H2NH2)2 and O SlCgH5CH2NH2 Examples ofmetal carboxylates which are operable in this invention are such ascadmium octoate, cadmium acetate, zinc octoate, potassium acetate, leadstearate, co balt octoate, cobalt naphthenate, magnesium octoate, leadoctoate, magnesium naphthenate and lead hexoate. Examples of organicesters of titanium and zirconium are tetraethyltitanate,tetraisopropyltitanate, tetraisopropylzirconate, tetraoctyltitanate,tetraocadecylzirconate, octylene glycol titanate, glycerol titanate,triethanolamine titanate, titanium lactate and zirconium lactate.Examples of the alkyl tin carboxylates are diethyltin diacetate,tributyltin propionate, dibutyltin dilactate, butyltin trioctoate,trioctadecyltin diacetate, trimethyltin stearate, dibutyltin dibenzoateand dibutyltin diacetate. The catalyst can be used 8 in amounts normallyused in curing siloxane systems such as from 0.01 to 10 weight percentbased on the total weight of the siloxane copolymer.

The following examples are illustrative only and should not be construedas limiting the invention which is properly delineated in the appendedclaims.

Example 1 A mixture of 60 grams of a trimethylsilyl endblockedmethylhydrogenpolysiloxane having a viscosity of 32.9 cs. at 25 C., 180grams of r CH =CHSi0Si(C1I3)a H1 and 0.2 gram of a mixture of one weightpercent platinum on charcoal was heated to 180 C. and allowed to refluxfor 2.5 hours. The mixture was then cooled to room temperature andfiltered twice by vacuum through an exceptionally pure diatomaceoussilica, known as Super-Cel made by Celite. The product contained 73.7mol percent of (IJH on; OSiCIIzCHzSiOSKCIIa):

CH units and about 26.3 mol percent of III CH SiO units and had aviscosity of 3,369 cs. at 25 C.

A solution of 3.5 g. of the above siloxane copolymer, 120 ml. ofperchloroethylene and 0.3 g. of

was applied to tan sateen by dipping the fabric into the solution andthen padding. The treated fabric was air dried and thereafter cured for3 minutes at 176 C. The treated fabric showed a spray rating of 100. Thewater repellency of the cured fabric Was determined by using the sprayrating test as defined by ASTM D583-58 or the spray test of AATCCStandard Test Method 221961.

Example 2 A mixture of 76.4 g. of CH =CHSi[OSi(CH and 0.1 g. of amixture of 1 weight percent platinum on charcoal was placed in a 500 ml.flask equipped with a dropping funnel, an agitator and a refluxcondenser and then heated to 120 C. At 120 C. a trimethylsilylendblocked methylhydrogenpolysiloxane was slowly added to the silanemixture. After the polysiloxane was added the mixture was refluxed for 6hours at 200 C. The mixture was cooled to room temperature and 100 ml.of toluene was added. The product was filtered through an exceptionallypure diatomaceous silica. The filtered product was stripped up to 165 C.at 5 mm. Hg. The product had 98.9 mol percent of A solution of 120 ml.of perchloroethylene, 3 g. of the above siloxane copolymer and 0.3 g. of

was applied to x 80 cotton print fabric by dipping and then padding. Thetreated fabric was air dried and then cured for 3 minutes at 176 C. Aspray rating of was obtained as determined by the procedure of Example1.

Example 3 The durability of the Water repellent treatment on the fabricswas determined by observing the water repellent Example 4 When thefollowing silanes and silicon hydride polysiloxanes in the indicatedratios are reacted according to the procedure of Example 1, siloxanecopolymers are obtained.

Silane Moles of silane per Silicon hydride polysiloxane molecular weightof silicon hydride polysiloxane CHQCH;

OH; CH3 H CH; 1 CHFCHCHgSi-OSKCHs): HzSiO[( iO)o(SiO)1r4]S!iH2 2 Ha CH;H;

( tHOI CgHs H CH3 (H5)2 2 OHFCHS iIOSKCQHOah OHaSiO[(iOnMSiOhflSiCH; 30

oHs CHzCHzCFz CHzCHzCFa CHzCHzCFs 0511s 3 CHFCHSiOSi(CHzCH2OF3)3HzSi0[(SiO)4o (SiO)4lSiHz (IJH: III (1H3 CAHB H 4CHFCH(CHz)zSl[OBl(CH3)2]: (S iO) 4 1 6H; l

OH; H 6 OHFCHCH SHOSKCHahh (CHa)aSi0( i0)2uaaSi(CHa)z 4 H H 6CHFCHSi[OSi(C4HzBt)3h CHAlOKSiOh flS F-CH 198 H CoHs CaHu CH3 7 CHFCHSHOSKCHzCHzCHQa]; (CH3) 810[(SiiO)2o( iO) ]Si(OHs)a 4 CuH O H 8 CH=CHSiO-SiCH2CHa siloxaue Copolymer composed of 20 mol percent 1 15 I ICHzSiO units, mol percent CeHlClSiO units,

| 20 mol percent CH3OH2Sio units, 20 mol percent (CHa)2SiO units, 10 molpercent CHa(CH2)aSiO units, 10 mol percent (CHmSiO units.

1 Mol percent.

Initial Spray ratings after-- Siloxane spray copolymer rating 1 3 5laundering launderings launderings Example 1 100 80-90 70 70 Example 2100 80 70 70 Example 5 When a perchloroethylene solution of the siloxauecopolymer of Example 2 is applied to paper, glass, leather, wood andconcrete blocks, a water repellent product is formed when cured at 205C. for 2 minutes.

Example 6 When an emulsion is prepared from water, toluene, a nonionicsurfactant, the siloxane copolymer of Example 4, No. 3, and titaniumlactate and is applied to concrete building blocks and then heated to260 C. for 5 minutes, a water repellent product is formed.

Example 7 When hexylamine, diethylamine, zinc octoate,tetraisopropylzirconate, triethanolamine titanate, dibutyltin 1 1dilactate, dibutyl in diacetate or cobalt naphthente is substituted for(CH O) SiCI-I CH CH NHCH CH NH in Example 1, equivalent results areobtained.

Example 8 When paper is sprayed with a mist from a consumer aerosolpackage wherein the mist consists of the siloxane copolymer of Example4, No. 5, chlorothene, dichlorodifluoromethane, and dibutyltindiacetate, a water repellent paper is obtained when cured for 10 minutesat 65 C.

That which is claimed is:

1. A siloxane copolymer of the general formula R is a monovalent radicalselected from the group consisting of alkyl radicals having from 1 to12, inclusive, carbon atoms, halogenated alkyl radicals having from 3 to12, inclusive, carbon atoms, phenyl radicals and halogenated phenylradicals,

R is a monovalent radical selected from the group consisting of alkylradicals having from 1 to 6, inclusive, carbon atoms, halogenated alkylradicals having from 3 to 6, inclusive, carbon atoms, phenyl radicalsand halogenated phenyl radicals,

a has an average value of from to 2, inclusive,

b has a value from 2 to 4, inclusive,

m has a value such that at least 2 mol percent of the silicon atoms haveat least one radical and not more than 99 mol percent of the siliconatoms have at least one n has a value such that at least 1 mol percentof the silicon atoms have at least one hydrogen atom bonded to a siliconatom and not more than 98 mol percent of the silicon atoms have at leastone hydrogen atom bonded to a silicon atom,

z has an average value of from 0 to a maximum value which is such thatnot more than 97 mol percent of the silicon atoms have 2 -R radicals persilicon atom,

the sum of m+n+z is from 6 to 2,000,

x has an average value of from 0 to 2, inclusive,

y has an average value of from 0 to 2, inclusive,

the sum of x+y is from 0 to 2, inclusive, and

d has a value of from 0 to 2, inclusive.

2. A siloxane copolymer in accordance with claim 1 wherein d is 0.

3. A siloxane copolymer in accordance with claim 1 wherein d is 2.

4. A siloxane copolymer in accordance with claim 1 wherein a is 0.

5. A siloxane copolymer in accordance with claim 1 wherein z is 0.

6. A siloxane copolymer in accordance with claim 1 wherein the sum ofm+n+z is from 10 to 200.

7. A siloxane copolymer in accordance with claim 1 wherein b is 2.

8. A siloxane copolymer in accordance with claim 1 wherein each R and -Ris a methyl radical.

9. A siloxane copolymer in accordance with claim 8 wherein the sum ofm+n+z is from 10 to 200.

10. A siloxane copolymer in accordance with claim 9 wherein d is 2, z is0, b is 2, x is 0 and y is O.

1 1. A siloxane copolymer in accordance with claim 1 wherein m has avalue such that at least 25 mol percent of the silicon atoms have atleast one -(OH ,SiR (OSiR' radical and not more than mol percent of thesilicon atoms have at least one (C-H SiR,,(OSiR radical, 11 has a valuesuch that at least 25 mol percent of the silicon atoms have at least onehydrogen atom bonded to a silicon atom and not more than 75 mol percentof the silicon atoms have at least one hydrogen atom bonded to a siliconatom and z is 0.

'12. A siloxane copolymer of the formula ornoinsqosuoumh wherein theratio of mm is from 2:3 to 3:2 and the sum of m+n is from 10 to 200.

References Cited UNITED STATES PATENTS 8/1966 Holbrook 260-46.5 9/1967Holbrook 260448.2

U.S. Cl. X.R.

1l7l6l, 143, 124, 138.8, 144; 260448.2, 29.1, 32.8, 33.8, 33.4, 18

